全文获取类型
收费全文 | 2976篇 |
免费 | 99篇 |
国内免费 | 9篇 |
专业分类
化学 | 1988篇 |
晶体学 | 26篇 |
力学 | 85篇 |
数学 | 368篇 |
物理学 | 617篇 |
出版年
2023年 | 26篇 |
2022年 | 35篇 |
2021年 | 94篇 |
2020年 | 72篇 |
2019年 | 64篇 |
2018年 | 71篇 |
2017年 | 52篇 |
2016年 | 132篇 |
2015年 | 93篇 |
2014年 | 111篇 |
2013年 | 177篇 |
2012年 | 169篇 |
2011年 | 217篇 |
2010年 | 148篇 |
2009年 | 118篇 |
2008年 | 166篇 |
2007年 | 146篇 |
2006年 | 128篇 |
2005年 | 98篇 |
2004年 | 106篇 |
2003年 | 81篇 |
2002年 | 78篇 |
2001年 | 50篇 |
2000年 | 40篇 |
1999年 | 25篇 |
1998年 | 25篇 |
1997年 | 28篇 |
1996年 | 31篇 |
1995年 | 18篇 |
1994年 | 23篇 |
1993年 | 24篇 |
1992年 | 32篇 |
1991年 | 23篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 10篇 |
1986年 | 9篇 |
1985年 | 13篇 |
1984年 | 12篇 |
1983年 | 11篇 |
1981年 | 16篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1976年 | 10篇 |
1972年 | 11篇 |
1918年 | 8篇 |
1901年 | 11篇 |
1885年 | 9篇 |
排序方式: 共有3084条查询结果,搜索用时 31 毫秒
41.
Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending
on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient,
give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This
review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry
(FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS),
Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and
atom trapping mechanisms are presented.
Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970
Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br
Received December 20, 2001; accepted October 11, 2002 相似文献
42.
The structure of the hydrogenation product of barbatusin, a diterpenoid from Coleus barbatus Bentham has been revised on the basis of NMR and X-ray data. A geminal coupling of unusually high magnitude has been observed and analysed. 相似文献
43.
E. M. Telles J. C. S. Moraes A. Scalabrin D. Pereira G. Carelli C. A. Massa A. Moretti F. Strumia 《International Journal of Infrared and Millimeter Waves》1995,16(12):2233-2248
We used a Stark-Optoacoustic cell and hybrid waveguide resonators to perform an Infrared and Far Infrared Stark Spectroscopy study on some transitions of13CD3OH. Different behaviours of the transitions in the presence of a d.c. electric field were observed. The Stark splittings of six FIR laser lines ranging from 34 to 136 MHz/kVcm–1 were determined. The analysis of the behaviour of the IR and FIR transitions in the presence of the external electric fields gives important and exclusive information on the levels involved in the transitions.Work Supported by FAPESP, CNPq, FAEP - Brazil, and CNR - Italy. 相似文献
44.
van Nostrum CF Benneker FB Brussaard H Kooijman H Veldman N Spek AL Schoonman J Feiters MC Nolte RJ 《Inorganic chemistry》1996,35(4):959-969
The synthesis of novel magnesium, copper, and metal-free porphyrazines, peripherally substituted with dithia-7-crown-2 (MPz(7)), dithia-15-crown-5 (MPz(15)), and dithia-18-crown-6 (MPz(18)) macrocycles is reported. These compounds are prepared starting from dicyanoethylene containing crown ethers 3, 2(1), and 2(2), respectively, which contain sulfur as well as oxygen heteroatoms. The "crowned" porphyrazines bind silver(I) and mercury(II) perchlorates. UV/vis spectroscopy and electron paramagnetic resonance measurements reveal that addition of the transition-metal ions leads to dimerization of the porphyrazine complexes. In the case of the dithia-18-crown-6-substituted porphyrazines, the dimers break up to form monomeric 6:1 guest-host complexes when more than 2 equiv of the metal ion is added. The single-crystal structures of the crown ether 2(2) and the porphyrazine MgPz(18) are presented. Compound C(14)H(20)N(2)O(4)S(2) (2(2)) crystallizes in the monoclinic space group P2(1)/c with a = 10.9310(13) ?, b = 19.383(3) ?, c = 8.6976(14) ?, beta = 108.898(11) degrees, V = 1743.5(5) ?(3), and Z = 4. The structure refinement converged to R = 0.0366 and R(w) = 0.0504. Compound C(56)H(82)MgN(8)O(17)S(8) (MgPz(18)) crystallizes in the triclinic space group P&onemacr; with a = 9.584(3) ?, b = 17.672(2) ?, c = 19.620(4) ?, alpha = 84.904(14) degrees, beta = 85.21(2) degrees, gamma = 89.29(2) degrees, V = 3298.4(13) ?(3), and Z = 2. The structure refinement converged to R1 = 0.0839 and wR2 = 0.2196. The electrical properties of H(2)Pz(18) have been studied by complex impedance spectroscopy. The bulk electrical conductivity of this compound is approximately 1 order of magnitude higher than that of the corresponding 18-crown-6 phthalocyanine. 相似文献
45.
46.
Rigol C Olea-Azar C Mendizábal F Otero L Gambino D González M Cerecetto H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):2933-2938
Cyclic voltammetry and electron spin resonance (ESR) techniques were used in the investigation of several potential antiprotozoal thiosemicarbazones nitrofurane derivatives. A self-protonation process involving the protonation of the nitro group due to the presence of an acidic proton in the thiosemicarbazone moiety was observed in the first step of a CEE(rev) reduction mechanism of these derivatives. ESR spectra of the free radicals obtained by electrolytic reduction were characterized and analyzed. AM1 methodology was used to obtain the optimized geometries and UB3LYP calculations were performed to obtain the theoretical hyperfine coupling constants. The theoretical study exhibited an unusual assignment of the spin densities showing a free radical centered in the thiosemicarbazone moiety rather than the nitro which are in agreement with the experimental hyperfine pattern. 相似文献
47.
A general approach for the allylation of aldehydes using stable, air-tolerant camphor-based chiral allylboronates under Sc(OTf)3 catalysis is described. This practical methodology provides both syn and anti propionate units and other homoallylic alcohols with very high levels of diastereo- and enantioselectivity for several substrates, including functionalized aliphatic aldehydes useful toward the elaboration of complex natural products. 相似文献
48.
Stephan Weinbruch Michael Wentzel Manfred Kluckner Peter Hoffmann Hugo M. Ortner 《Mikrochimica acta》1997,125(1-4):137-141
In this paper procedures for the characterization of individual aerosol particles by element mapping in the electron microprobe are presented. The number, size and qualitative chemical composition of particles is derived from a combination of secondary or backscattered electron images and element distribution maps. Accuracy of the size distribution and reliability of the qualitative analysis procedure were checked with silicate samples. In order to obtain a semi-quantitative estimate of the chemical composition of individual particles the count rates taken from element distribution maps are corrected for matrix and geometric effects using particle ZAF procedures.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
49.
Pedro A. Fernandes Elsa S. Henriques Vineet Pande Maria. J. Ramos Ana R. R. Maia André A. S. Almeida Bruno F. B. Silva Carla M. S. Ribeiro César F. B. Ribeiro David S. M. Ribeiro Diana A. P. Fonseca Eva M. S. Cunha Filipe R. N. C. Maia Joana A. A. Pereira João P. G. Pacheco Joaquim A. A. D. Ferreira Liliana R. C. Matos Manuel A. B. P. Pinto Maria C. S. Borges Paulo J. C. R. Magalhães Pedro F. R. D. Teixeira Pedro N. B. C. Veloso Ricarte J. F. Ferreira Sandro S. Gomes Tiago F. Barros Tiago S. J. T. Selão Virgínia M. M. C. Fernandes 《Theoretical chemistry accounts》2005,113(4):197-204
We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-12,14 -prostaglandin J2 (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs. 相似文献
50.
Hugo M. Ortner 《Fresenius' Journal of Analytical Chemistry》1992,343(11):825-826
Conclusion Analytical Chemistry, as we have seen, is quite an established science but also a very vivid and young one. Its boundaries have always been and will be at the very frontiers of natural science: we are approaching the detection of single atoms as well as the analysis of matter at the very fringes of our universe. Analytical Chemistry is essential for the development of taylor-made high-tech materials and equally for the evolution of our knowledge about the toxicity of elements and compounds. It needs specialists with a profound insight in certain fields, for methods development or the handling of very complex instrumentation as e.g. a high resolution secondary ion mass spectrometer. But it also needs allrounders with a broad view not only of the capability of Analytical Chemistry as a whole but with an understanding for the complexity of modern social and economic structures. Frequently new ideas, new concepts and progress are forming on the seams between disciplines, on the grain boundaries of scientific fields too often kept strictly separated from each other. Analytical Chemistry is certainly a discipline which is predestinated for scientific communication collaborating with practically all fields of natural science as well as politics and economics.As a branch of natural science it is neutral in its moral value and therefore needs responsible and courageous analysts to use it for the benefit of mankind. 相似文献